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Theoretical Insights into Intracrystalline Diffusion of Olefins in MTO Catalysts

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Abstract

Diffusion process plays a decisive role in MTO reactions over zeolite catalysts. In this work, a theoretical approach was developed for modelling olefins diffusion in two typical zeolites, HZSM-5 and HSAPO-34. Activation barrier between large cavities and channels was determined using Lennard–Jones (LJ) potentials, where electrostatic potential was inserted to account for the induced dipole force that had been ignored in previous studies. Six typical products of MTO were selected as probe molecules. Detailed insights into the variation of activation barrier and diffusivity were obtained via comparative analysis between the two zeolites. Transition from Knudsen diffusion to configurational diffusion was also discriminated, and probe molecules were found to fall basically either in configurational regime or near transition regime. This work provides a submodel for further modeling of the complete reaction system, and ultimately contributes to a rational design of zeolite catalysts.

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Abbreviations

d c :

Channel and window diameter inside HZSM-5 and HSAPO-34, Å

d i :

Cage and intersection diameter of HZSM-5 and HSAPO-34, Å

d m :

Molecular kinetic diameter, Å

d o :

Oxygen diameter, Å

d w :

Distance from window/channel wall, Å

D :

Intracrystalline diffusivity, M2/s

D k :

Knudsen diffusion coefficient, m2/s

E a :

Activation Energy, kJ/mole

f :

Orientation probability coefficient

k :

Boltzmann Constant, J/K

L :

Length of channel and window, m

M :

Molecular mass, kg

q :

Charge on hydrogen of bronsted site, eV

r :

Distance between guest molecule and native site, Å

R:

Ideal gas constant, J/mol. K

R c :

Distance between centres of channel/window and nuclei of surface oxygen, Å

R i :

Distance between centres of intersection/cage and nuclei of surface oxygen, Å

T :

Temperature, K

V c :

Potential in window/channel of HSAPO-34 and HZSM-5, kJ/mole

V e :

Electrostatic potential, kJ/mole

V i :

Potential inside cage/intersection of HSAPO-34 and HZSM-5, kJ/mole

Z :

Coordination number of zeolites

α:

Mean molecular polarizability, Å3

ε:

Permittivity of medium, for zeolite it is almost equal to 1

εo :

Vacuum permittivity

μ:

Dipole moment, C. m

\(\overline{V}\) :

Molecular diffusional mean velocity, m/s

εm :

Lennard Jones potential constant for individual molecule, KJ/mole

εmo :

Lennard Jones potential constant for molecule-oxygen pair, KJ/mole

σc :

σI, Pairwise Lennard Jones potential length constant between molecule-oxygen pair inside channel/window, Å

σm :

Lennard Jones length constant, Å

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Acknowledgements

This work is financially supported by the 2019 Key Technology Project of Inner Mongolia, China.

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  1. Department of Chemical Engineering, Shanghai Jiao Tong University, Shanghai, 200240, China

    Khizar Hayat, Xue-Gang Li & Wen-De Xiao

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  1. Khizar Hayat
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  2. Xue-Gang Li
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  3. Wen-De Xiao
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Correspondence to Xue-Gang Li.

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Hayat, K., Li, XG. & Xiao, WD. Theoretical Insights into Intracrystalline Diffusion of Olefins in MTO Catalysts. Catal Lett 150, 2056–2067 (2020). https://doi.org/10.1007/s10562-020-03136-9

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